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Abstract
The influence of interface structure between Nafion and an electrode surface on cathodic oxygen reduction has not been fully
clarified yet in spite of the need for improving the performance of polymer electrolyte fuel cells (PEFCs) by clarifying the influence.
In the present study, oxygen reduction was investigated at the interface between Nafion and a glassy carbon (GC) surface where
the ratio of the fluorinated region in Nafion contiguous with the GC surface was controlled by electrochemical oxidation of the
GC surface. Measurements of the oxygen reduction current were carried out using rotating GC disk electrodes and those covered
with Nafion , and the kinetic currents were determined for these electrodes. The surface oxidation resulted in an increase in the
oxygen reduction current both at bare GC and Nafion -coated GC; thus, the ratio of the kinetic current at the latter to that at the
former was used for evaluating the effect of change in the interface structure between Nafion and the GC surface. The net current
ratio that was calculated by dividing the kinetic current ratio by the ratio of the GC surface contiguous with the ionic cluster region,
where electrode reactions occur at the Nafion -coated electrodes, increased with a decrease in the blocking of the GC surface by the
fluorocarbon region; while excessive reduction of the region reduced the ratio. This result indicates the possibility of optimization of
the Nafion j electrode interface for O2 reduction by controlling the ratio of the electrode surface contiguous with the fluorocarbon
region. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: PEFC; Oxygen reduction; Nafion ; Glassy carbon; Surface oxidation; Rotating disk electrode
1. Introduction
Cathodic oxygen reduction has long been studied
particularly due to its involvement in energy conversion
processes. Recently, it has attracted considerable attention as the cathode reaction of polymer electrolyte fuel
cells (PEFCs), which are one of the most attractive
power sources of clean energy and are expected to be
used in electric vehicles, portable power generators, onsite cogeneration systems, and so on [1 /4]. The slow
reaction rate of O2 reduction at the PEFC-operation
temperature causes a large cell voltage loss of 0.4 /0.5 V
at a current density of 1 A cm 2 [5]. This problem has to
be overcome to realize the practical use and prevalence
of PEFCs.
The electrode reactions of the PEFC occur in the gasdiffusion electrode at the interface between the surface
of dispersed Pt particles and the polymer electrolyte
because it covers the Pt-supporting carbon catalyst
particles and forms pathways of proton conduction in
the gas-diffusion electrode, which leads to enlargement
of the three-phase zone [6 /9]. A number of reports have
appeared on the O2 reduction at the Pt j polymer
electrolyte interface to clarify the interfacial reaction
kinetics using smooth Pt electrodes [10 /13] or microelectrodes [14 /18] coated with perfluorosulfonate cation-exchange membranes such as Nafion . Gottesfeld
et al. [10], Lawson et al. [11], and Floriano et al. [12]
reported that the kinetic currents for O2 reduction at
Nafion -coated Pt electrodes are larger than those at
bare Pt in aqueous solutions. Such an enhancement
effect of the Nafion coating has been explained by the
fact that the solubility of oxygen in Nafion is higher
than in aqueous solutions, which is mainly due to the
presence of the hydrophobic fluorocarbon phase; it is
0022-0728/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 2 ) 0 0 8 2 7 - 6
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2. Experimental
Detailed description of the electrochemical measurement system including reagents, a cell, and apparatus
was given in Ref. [25]. The GC electrode (BAS) was a
rotating disk electrode (RDE) which consisted of a GC
rod (Sigradur G, made from phenolic resin through
solid phase pyrolysis at 1100 8C followed by hightemperature treatment up to 2200 8C) sealed in a Kel-F
holder. The geometric surface area of the electrode was
0.071 cm 2 (3 mm in diameter). Its surface was polished
with a 0.05-mm alumina suspension on a polishing cloth
(Maruto Instrument) and then cleaned ultrasonically in
high-purity water. Electrochemical surface oxidation of
GC and subsequent Nafion -coating were carried out
in the same way as in Ref. [25]. The surface oxidation
was carried out by holding the GC electrode potential at
2.0 V versus a reversible hydrogen electrode (RHE) for
various lengths of time in 0.5 M H2SO4 at 25 8C. The
thickness of the Nafion film was 0.98 mm when wetted,
which was calculated from the mass of recast Nafion
solution, the surface area, and the hydrated Nafion
density (1.58 g cm 3) [26,27]. Here, the assumption was
made that the recast film swells essentially in the
direction perpendicular to the surface [10].
Cyclic voltammograms were recorded in 0.5 M H2SO4
at 25 8C for surface-oxidized GC electrodes and those
coated with Nafion to obtain the ratio of the ionic
cluster region to the total GC surface. The potential was
scanned between 0.05 and 1.4 V at a scan rate of 50 mV
s 1. Before recording, the potential was scanned
repeatedly in the same range to remove residual
impurities. The ratio of the GC surface contiguous
with the ionic cluster region to the total GC surface, uic,
was estimated using the following equation
uic
Qf
Q
(1)
(2)
Current /potential relations were measured in O2 saturated 0.5 M H2SO4 at 25 8C for surface-oxidized
GC RDE and that coated with Nafion at several
rotation speeds. The scan rate of the disk potential was
fixed at 10 mV s 1. Prior to the each measurement, the
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68
(3)
Fig. 4. Tafel plots of kinetic current per unit geometric surface area at
bare GCs. GC surface-oxidation time: 0 (k), 1 (m), 5 (I), and 20 min
(m).
Fig. 5. Tafel plots of kinetic current per unit geometric surface area at
Nafion -coated GCs. GC surface-oxidation time: 0 (k), 1 (m), 5 (I),
and 20 min (m).
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70
4. Conclusions
RDE measurements were carried out for cathodic O2
reduction at surface-oxidized GC electrodes and those
coated with Nafion where the ratio of the GC surface
contiguous with the ionic cluster region was changed.
The kinetic current for O2 reduction increased with an
increase in surface-oxidation time both at bare GC and
at Nafion -coated GC; while the latter needed a longer
surface-oxidation time than the former to show the same
current. There are two possible reasons for the fact that
the current was smaller at Nafion -coated GC than at
bare GC. One is the higher pH environment for O2
reduction at Nafion -coated GC because the activity
for O2 reduction at the carbon electrode decreases as the
pH decreases. The other is the blocking of the GC
surface by the side chains of the Nafion polymer in the
ionic cluster region, caused by the interaction between
the fluorocarbon part of the side chains and the GC
surface having a hydrophobic character.
The ratio of the kinetic current at Nafion -coated
GC to that at bare GC showed the dependence of O2
reduction on the ratio of the GC surface contiguous
with the fluorocarbon region of Nafion to the total
GC surface. When the current ratio was divided by the
ratio of the ionic cluster region to derive the net current
ratio, it increased slightly with an increase in the ratio of
the fluorocarbon region up to 0.24 and decreased with a
further increase in the ratio. This increase is attributed
to the presence and the change in the number of active
sites for O2 reduction that lie immediately adjacent to
the fluorocarbon region and benefit from the high O2
concentration in the region. The decrease could be
explained by the adsorption of the side chains of
Nafion polymer in the ionic cluster region, which
was due to the increasing hydrophobicity of the GC
surface. This result indicates the possibility of optimization of the Nafion j electrode interface for O2 reduction by controlling the ratio of the electrode surface
contiguous with the fluorocarbon region.
References
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